Substituted aromatic silane compounds and method for preparation of same

ABSTRACT

A new group of silane compounds in which silicon atoms are linked together by a hydrocarbon chain and which comprise phenyl groups substituted with an epoxy group or an ethenyl group. The compounds of the present invention have the formula ##STR1## where R 1  is selected from the group consisting of: (a) an aliphatic hydrocarbon group containing 2 to 10 carbon atoms, and 
     (b) a group having the formula ##STR2##  where n=1 to 3 
     m=0 to 5; 
     R 2  and R 2  &#39; are each selected from the group consisting of an alkyl group containing 1 to 4 carbon atoms, an unsubstituted aryl group, and a substituted aryl group; and R 3  is selected from the group consisting of: ##STR3## where R 4 , R 5 , and R 6  ae each selected from the group consisting of H, an alkyl group containing 1 to 4 carbon atoms, and an aryl group; and n=0 to 10.

This is a division of application Ser. No. 07/046,013, filed May 5,1987, now U.S. Pat. No. 4,861,901.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates generally to silicon-containingsubstituted aromatic compounds. More particularly, the present inventionrelates to compounds comprising silicon atoms linked together by ahydrocarbon chain and further comprising phenyl groups substituted witha glycidyl group or an allylic group.

2. Description of the Background Art

Epoxy resins are widely used as adhesives, encapsulants, and coatingsfor a variety of applications. In particular, for application tostructural and electronic devices, epoxy resins are useful since theyprovide mechanical protection, good substrate adhesion, thermal andoxidative stability, and moisture and solvent resistance. In addition,compliance is a highly desirable property for these resins since itallows the dissipation of stress that accompanies thermal and mechanicalcycling of the encapsulant. Furthermore, enhanced toughness providesmechanical protection against fracture damage. However, state-of-the-artsystems exhibiting such compliance generally possess poor thermalstabilities. Another important property is the repairability of theadhesive, coating, or encapsulant. As expected, a rigid system isgenerally more difficult to repair and replace than a ductile one.

One group of epoxy resins particularly useful for electronicapplications consists of epoxysilicone compounds, which are compoundscomprising silicon atoms joined together by oxygen linkages and furthercomprising terminal glycidyl groups. Such epoxysilicone compounds havebeen known for many years and are described, for example, in thepublications by Bilow, Lawrence and Patterson, "Synthesis andPolymerization of 1,3-bis(2,3-epoxypropylphenyl)tetramethylsiloxanes andRelated Compounds, Journal of Polymer Science, Volume 5, 1967, pages2595 to 2615 and by Patterson and Bilow, "Polymers fromSiloxane-Containing Epoxides," Journal of Polymer Science, Volume 7,1969, pages 1099 to 1110. As described in these references, suchepoxysiloxane compounds were prepared by reacting the Grignard reagentderivable from an allybromobenzene with a large excess ofdichlorodimethylsilane. The resulting compound,chlorodimethyl(allyphenyl)silane, must be isolated from excessdichlorodimethylsilane by repeated distillation steps.Chlorodimethyl(allylphenyl)silane was then hydrolyzed to give1,3-bis(allyphenyl)-1,1,3,3-tetramethyl-1,3-disiloxane. Epoxidation waseffected either with 3-chloroperoxybenzoic acid or trifluoroperoxyaceticacid. However, such a procedure is not only tedious, but also yields aproduct contaminated by impurities produced by rearrangement orreversion in which --Si--O-- groups break away from the rest of themolecule and form macrocycles or higher linear chains. In addition, thecorrosive trifluoroperoxyacetic acid was difficult and dangerous toprepare on a large scale, and the 3-chlorobenzoic acid side productgenerated in the epoxidation reaction was so soluble in the desiredproduct that complete removal of this acid residue was impossible.Furthermore, such a process is not conducive to tailor making the lengthof the siloxane chain.

When epoxy resins are used in structural applications for outer space,such as for adhesives or coatings in satellite components, the resinmust not only be able to withstand the temperature extremes encounteredin space, for example -148° F. (-100° C.) to 212° F. (100° C.), forextended periods of time, such as several years, but also be able towithstand the higher temperatures (350° F. or 177° C.) encountered inrigorous space applications for shorter periods of time. In addition,the material must meet the National Aeronautics and Space Administration(NASA) outgassing requirements, i.e., < 1% total mass loss, and ≦ 0.10%collectible volatile condensable materials, to insure that the materialdoes not release gaseous component substances which would undesirablyaccumulate on other spacecraft parts in the outer-space vacuum.Heretofor, ductile, processible epoxy resins meeting all theserequirements have been unobtainable.

Thus, a need exists for an epoxy resin for electronic and structuralspace applications which is tough, thermally and oxidatively stable,repairable, resistant to moisture and solvents, and which possesses lowoutgassing characteristics. In addition, a need exists for thepreparation of the ψ, ω-alkenyl compounds from which such epoxy resins,among others, may be formed. The next to the lowest homolog of the ψ,ω-alkenyl group is the allyl group from which the glycidyl group isderived.

SUMMARY OF THE INVENTION

The general purpose of the present invention is to provide new andimproved silicon-containing substituted aromatic compounds. Thesecompounds possess most, if not all, of the advantages of the above priorart compounds while overcoming their above-mentioned significantdisadvantages.

The above-described general purpose of the present invention isaccomplished by providing a new group of silane compounds in whichsilicon atoms are linked together by a hydrocarbon chain and whichcomprise phenyl groups substituted with a glycidyl-terminated alkylgroup or a ψ,ω-alkenyl group. The compounds of the present inventionhave the formula ##STR4## wherein: R₁ is selected from the groupconsisting of:

(a) an aliphatic hydrocarbon group containing 2 to 10 carbon atoms, and

(b) a group having the formula ##STR5## where n=2 to 3

m=0 to 5;

R₂ and R_(2') are each selected from the group consisting of an alkylgroup containing 1 to 4 carbon atoms, an unsubstituted aryl group, and asubstituted aryl group; and

R₃ is selected from the group consisting of: ##STR6## where R₄, R₅, andR₆ are each selected from the group consisting of H, an alkyl groupcontaining 1 to 4 carbon atoms, and an aryl group; and

n=0 to 10.

Accordingly, it is a purpose of the present invention to provide epoxyresins for use as adhesives, encapsulants, or coatings, which are tough,compliant, thermally and thermo-oxidatively stable, and resistant tomoisture and solvents.

Another purpose of the present invention is to provide epoxy resins ofthe type described which further possess low outgassing characteristicsand are suitable for space applications.

A further purpose of the present invention is to provide a process forforming the above-described epoxy resins in high purity.

Still another purpose of the present invention is to provide themonomers from which the above-described epoxy resins may be prepared.

Another purpose of the present invention is to provide a process forforming the above-described epoxy monomers in high purity.

Yet another purpose of the present invention is to providesilicon-coating difunctional ψ,ωalkenyl monomers for use in formingpolymers which are tough, compliant, thermally and thermo-oxidativelystable, and resistant to moisture and solvents.

Another purpose of the present invention is to provide a process forforming the above-described difunctional ψ,ω-alkenyl monomers in highpurity.

Still another purpose of the present invention is to provide polymers ofeach of the above-described monomers.

Another purpose of the present invention is to provide copolymers ofeach of the above-described monomers in which the flexibility anddimensional stability of the copolymer can be controlled andpredetermined.

A further purpose of the present invention is to provide a coating whichis resistant to abrasion by mechanical means or by plasma.

The foregoing and other objects, features, and advantages of the presentinvention will be apparent from the following more particulardescription of the preferred embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

Compounds in accordance with the present invention have the generalformula: ##STR7## where R₁ is selected from the group consisting of:

(a) an aliphatic hydrocarbon group containing 2 to 10 carbon atoms, and

(b) a group having the formula ##STR8## where n=1 to 3

m=0 to 5;

R₂ and R₂ ' are each selected from the group consisting of an alkylgroup containing 1 to 4 carbon atoms, an unsubstituted aryl group, and asubstituted aryl group; and

R₃ is selected from the group consisting of: ##STR9## where R₄, R₅, andR₆ are each selected from the group consisting of H, an alkyl groupcontaining 1 to 4 carbon atoms, and an aryl group; and

n=0 to 10.

The groups R₂ and R₂ ' may each be a C₁ to C₄ alkyl group or asubstituted or unsubstituted aryl group, such as phenyl, naphthyl,anthryl, or phenanthryl. It is anticipated that the fused aromaticgroups would impart unique photochemical properties to the compound inwhich they are incorporated. The phenyl group may be substituted with,for example, a methyl, carboxyl, or halogen group, and the substitutionmay be in the meta or para position with respect to the siliconattachment.

The group R₃ may be a glycidyl-terminated alkyl group, in which case themonomer is useful for forming epoxy resins as previously discussed. Thecompound of the present invention in which R₃ is a glycidyl-terminatedalkyl group is referred to herein as the "epoxy monomer." Alternatively,R₃ may be a ψ,ω-alkenyl group, in which case the monomer is useful forforming polymers and copolymers for application as low dielectricmaterials. The compound of the present invention in which R₃ is aψ,ω-alkenyl group is referred to herein as the "ethenyl monomer".

A preferred compound in accordance with the present invention is2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane where, in theabove formula, R₁ is --CH₂ --CH₂ --, R₂ and R₂ ' are each --CH₃, and R₃is a glycidyl-terminated methyl group attached to the benzene ring atthe position meta or para to the silicon attachment. Other preferredcompounds include homologs of the above-noted compound in which R₁ is aC₃ to C₁₀ aliphatic hydrocarbon group, most preferably (--CH₂ --CH₂ --)₃and (--CH₂ --CH₂ --)₄. Additional preferred compounds include thosehaving the above-noted formula in which R₁ is a C₂ to C₁₀ aliphatichydrocarbon group, R₂ is --CH₃, R₂ ' is --C₆ H₅, and R₃ is aglycidyl-terminated alkyl group. Thermal stability is enhanced in stillother preferred compounds in which a phenylene group is incorporated inthe straight chain between the silicon atoms, i.e., R₁, or in which oneof the two methyl groups on each silicon atom, i.e. R₂ or R₂ ', isreplaced by a phenyl group. Such preferred compounds have the formulanoted above with R₃ being a glycidyl-terminated alkyl group and in whichR₁ is --CH₂ --C.sub. 6 H₄ --CH₂ --, and R₂ and R₂ ' are each --CH₃, orin which R₁ is --CH₂ --C₆ H₄ --CH₂ --, R₂ is --CH₃, and R₂ ' is --C₆ H₅.Compounds corresponding to those noted above except having a ψ,ω-alkenylgroup, such as an allyl group, as R₃ are also preferred compounds inaccordance with the present invention.

Exemplary preparation of2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane and its allylprecursor is described in Example 1 herein. The homologs thereof areprepared in a similar manner by substituting the appropriateβ,ψ-dichloro-β,ψ-disilaliphatic reactant ##STR10## where n=an integer inthe Grignard synthesis step as described in Examples 6-7 and 10-12herein. Thus, by appropriate choice of the above-noteddichlorodisilaliphatic reactant, the internal chain length of the silanecompounds of the present invention can be pre-defined, which representsa significant advancement over the previously discussed prior artprocesses. The β,ψ-dichloro-β,ψ-disilaliphatic compounds of interest areeither commercially available or can be formed by known synthesismethods, such as referenced by T. L. Guggenheim, Tetrahedron Letters,volume 25, pages 1233-1254, 1984. As indicated in Example 4, the paraisomer of the compound described in Example 1 is obtained by substituted3-(4-bromophenyl-propene for 3-(3-bromophenyl)propene in the reactiondescribed in Example 1. The para isomer will lead to epoxy resins andpolymers derived from the ethenyl monomer that exhibit greaterdimensional stability, i.e., higher glass transition temperatures, thanthose derived from the meta isomers, while retaining acceptabletoughness characteristics.

The compound 2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane isprepared by reacting the Grignard reagent derived from3-(3-bromophenyl)propene and magnesium with2,5-dichloro-2,5-dimethyldisilahexane in anhydrous tetrahydrofuran toform 2,5-bis(3-allylphenyl)-2,5-dimethyl-2,5-disilahexane. The latter isthen allowed to undergo epoxidation with 3-chloroperoxybenzoic acid(MCPBA) to form 2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane.It has been found advantageous to use 3-chloroperoxybenzoic acid in theabove-noted epoxidation reaction since this compound is an inexpensiveand efficient epoxidation reagent and, further, since the side product,meta-chlorobenzoic acid, is not soluble in the epoxysilane product andtherefore can be virtually completely removed. Such is not the case inthe previous state-of-the-art syntheses of epoxysiloxanes, where thechlorobenzoic acid side product is soluble in the epoxy-silicone resin.This solubility of the benzoic acid side product makes isolation of thedesired epoxy-silicone product difficult and tedious. Thus, the presentinvention avoids this prior art problem. Another preferred oxidizingagent according to the present invention is trichloroperoxyimidic acid(TCPIA) generated in situ by the reaction of trichloroacetonitrile and30-50 percent hydrogen peroxide is a biphasic medium, such as water anddichloromethane.

The epoxy monomer compounds formed in accordance with the presentinvention may be cured with known curing agents such as1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl-1,3-disiloxane (known asAPMD), 1,3-bis-(3-aminobutyl)-1,1,3,3,-tetramethyl-1,3-disiloxane (knownas ABMD), triethylenetetraamine, meta-phenylenediamine,4,4'-methylenedianiline, diaminodiphenylsulfone, nadic methylanhydride,methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride,and 2-ethyl-4-methylimidazole, or other amine, amide, acid, andnitrogen-containing curing agents to form a resin. The term "resin" isused herein to mean a mixture of polymerizable materials either beforeor after polymerization.

The epoxy monomer compounds of the present invention may be polymerizedwith the above-noted epoxy curing agents to form homopolymers. Thesepolymers have been found to be very effective as abrasion-resistantcoatings, as discussed in Example 17. Alternatively, the present epoxymonomer may be copolymerized with other monomers to form thecorresponding copolymers. In particular, the epoxy monomer of thepresent invention may be copolymerized with commercially available epoxymaterials, such as DGEBA (the diglycidyl ether of Bisphenol A, availablefrom Shell Chemical), of which EPON 825 is an industry standard, epoxyphenol novalacs (such as DEN 438, available from Dow Chemical), epoxycresol novalacs (such as ECN 1235, available from Ciba Geigy) andtetraglycidylmethylene dianilines (such as MY 720, available from CibaGeigy), to improve the compliance of such materials. (The term"compliance" is used herein to mean the ability of an object to yieldelastically when a force is applied; flexibility).

In addition, the epoxy monomers of the present invention may becopolymerized with known silicone materials, such aspoly(dimethylsiloxanes), poly-(methylphenylsiloxanes), andpoly(diphenylsiloxanes), to provide crosslinking and network formationwhich provide dimensional stability. These commercial silicone materialsmay be obtained from Dow-Corning, Petrarch, and Silar, among others.

Thus, depending on the relative proportions of the epoxy monomer of thepresent invention and the material with which it is copolymerized (epoxyor silicone), a material of controlled and predetermined rigidity may beformed. The epoxy compounds of the present invention are used in theamount of 10 to 80 percent by weight of the mixture, preferably 30 to 50percent. The meta isomers of the epoxy monomers of the present inventionhave been found effective for increasing the flexibility of known epoxymaterials as described in Example 14. The para isomers of the epoxymonomers of the present invention have been found effective forincreasing the toughness of known epoxy materials as described inExample 15. ("Toughness" is used herein to mean the ability of amaterial to absorb energy by plastic deformation; being intermediatebetween soft and brittle.) Suitable curing agents for suchcopolymerization include: amino-functional siloxanes such as1,3-bis-(3-aminopropyl)-1,1,3,3-tetramethyl-1,3-disiloxane and1,3-bis-(3-aminobutyl)-1,1,3,3-tetramethyl-1,3-disiloxane; aliphaticamines, such as triethylenetetraamine, diethylenetriamine andmethanediamine; aromatic amines such as meta-phenylenediamine,4,4'-methylenedianiline, and diaminodiphenylsulfone; polyanhydrides suchas nadic methylanhydride, methyltetrahydrophthalic anhydride,methylhexahydrophthalic anhydride; and other standard epoxy curingagents.

The ethenyl monomer compounds formed in accordance with the presentinvention may be polymerized using known olefin polymerizationtechniques such as described in S. R. Sandler and W. Karo, "PolymerSyntheses", Volume III, Chapter 8, Academic Press, 1980 and H. G. Elias,"Macromolecules, Volume 2. Synthesis and Materials", Chapter 25, PlenumPress, New York, 1977. Such polymers have improved flexibility, thermaland thermo-oxidative stability and resistance to moisture and solvents,when compared to corresponding non-silicon-containing hydrocarboncompounds. In addition, the ethenyl monomer compounds of the presentinvention may be copolymerized with other materials, such asN-(vinylphenyl)phthalimide using known methods, such as described bySandler and Karo referenced above. Depending on the relative proportionsof the ethenyl monomer and the material with which it is copolymerized,a material of controlled and predetermined rigidity may be formed. Theethenyl compounds of the present invention are used in the amount of 10to 90 percent by weight of the mixture, preferably 30 to 70 percent.

Examples of practice of the present invention are as follows.

EXAMPLE 1

This example illustrates the preparation of2,5-bis(3-allylphenyl)-2,5-dimethyl-2,5-disilahexane and2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane in accordancewith the present invention.

A. Preparation of 3-(3-bromophenyl)propene:

In accordance with accepted laboratory practice, the glassware used forthe Grignard reaction described below was flame-dried and purged withdry nitrogen. A small portion of a solution of 118 g (0.50 moles) of1,3-dibromobenzene in 50 ml of anhydrous ether was added to 14.132 g(0.58 g-atom) of magnesium turnings in 150 ml of anhydrous ether. Thereaction started almost immediately to form the Grignard reagent. (Insituations where reaction does not proceed immediately, a few drops ofethyl iodide may be added to induce a reaction.) After a steady refluxwas established, the rest of the dibromobenzene solution was addeddropwise to maintain the reflux. The total addition required 45 minutes.The final mixture was heated for an additional hour. A solution of 46 mlof allyl bromide (65 g, 0.537 moles) in 50 ml of anhydrous ether wasadded dropwise. The final mixture was heated for an additional hour.

The mixture was poured into 1 liter of saturated aqueous ammoniumchloride solution, and the organic phase was separated. The aqueousphase was extracted with two 100-ml portions of ether. The etherealportions were combined, washed with 100 ml of water and dried overanhydrous magnesium sulfate. The concentrated filtrate was finallydistilled (60°-62° C./0.5 torr or 48°-50° C./0.1 torr) to yield 81.84 g(0.416 moles, 83.2%) of a clear liquid. Nuclear magnetic resonance (NMR)spectrometry showed a diagnostic splitting pattern of an allylic sidegroup and a characteristic (complex) meta-ring substitution,unequivocally establishing the identity of this product as the expected3-(3-bromophenyl)propene.

¹ H NMR(CDCl₃) 3.16, 3.28 (bd, 2H, benzylic H's), 4.82-5.22 (2 m, 2H,terminal H's on olefinic bond), 5.55-6.60 (broad complex multiplet, 1H,olefinic H), and 6.92-7.60 ppm (2 m, 4H, aromatic).

B. Preparation of 2,5-bis(3allylphenyl)-2,5-dimethyl-2,5-disilahexane:

The compound 2,5bis(3-allylphenyl)-2,5 dimethyl-2,5-disilahexene(Compound 3 below where n=1) was prepared in accordance with thefollowing reaction. ##STR11##

Into a flame dried reaction vessel under nitrogen were placed 10.45 g ofmagnesium (from Fluka Chemicals) and 150 ml of anhydrous tetrahydrofuran(THF) which was freshly distilled from sodium. An aliquot of a solutionof 85.5 g (containing 0.3875 moles of assay) of3-(3-bromophenyl)propene, Compound 1 above, prepared as described inStep A above, in 200 ml of anhydrous THF was added from the additionfunnel. The reaction started almost instantly. After the mixture reachedreflux, the addition was continued until all the reactant was added (1hr). The mixture was heated at reflux for 1 more hour and treated with asolution of 39.55 g (0.184 mole) of2,5-dichloro-2,5-dimethyl-2,5-disilahexane, Compound 2, n=1 above, fromPetrarch Chemicals, in 100 ml of anhydrous THF, added during reflux over0.5 hr. The reaction mixture obtained was heated further for another 1.5hr, cooled and stirred for 18 hours under nitrogen.

The mixture was poured into 1.5 liters of aqueous ammonium chloride andextracted with three 50-ml portions of diethylether. All organicfractions were combined, washed with water and dried over anhydrousmagnesium sulfate. After filtering and concentrating, the resulting oilwas distilled. The low boiling fractions collected (up to an oil bathtemperature of 150° C.) were shown to contain mono- and diallylbenzenes.The pot residue oil, which did not discolor, was shown to be the desiredproduct, Compound 3, where n=1 above, by its NMR absorptions showingperfect ratios of peak area integrations.

A second batch of Compound 3, where n=1 was prepared by the exactprocedure described above except that the dichlorosilane reactant,Compound 2, where n=1, was purified by distillation (at bp 198° C/734torr) before use. The distilled product, Compound 2, n=1, had a meltingpoint of 37° C.

Purification of the water white product oil of each batch was effectedby distillation under reduced pressure: bp 155° C./10⁻⁴ torr. (Theexternal heating oil bath reached a temperature of 220° C. but did notcause appreciable darkening of the product being distilled). At the endof the distillation, the pot residue was orange-brown and appeared to bemore viscous than before distillation. The NMR results for the productof the first batch were as follows: ¹ H NMR (CDCl₃): δ 0.25 (s, 12H,SiCH₃), 0.57 (s, 4H, CH₂ Si(CH₃)₃), 3.32, 3.43 (2 bs, 4H, 2 methylenes),4.97, 5.17 (2 bm, 4H terminal H's of olefin), 5.67-6.38 (m, 2H, vinylproton), and 7.30 ppm (bm, 8H, aromatics).

The ¹ H NMR results for the product of the second batch were the same asthose for the first batch. In addition, the following NMR results wereobtained for the product of the second batch.

¹ H NMR (250 MHz, CDCl₃): δ 0.29 (s, 12H), 0.73 (s, 4H), 3.40 (d, 4H,J=6.6 Hz), 5.07 (bs, 2H), 5.12 (d, 2H, J=7.8 Hz), 5.95-6.05 (Complex m,2H), and 7.17-7.38 ppm (Complex m, 8H).

¹³ C NMR (62.8 MHz, CDCl₃): δ -3.2, 8.1, 40.6, 116.3, 128.1, 129.4,131.7, 134.1, 137.8, 139.4 and 139.7 ppm (11 lines as expected).

Characterization of the purified product also included massspectrometry, infrared spectroscopy, elemental analysis and refractiveindex measurements.

Refractive index measured at 24° C.: 1.5361.

IR (Neat): 2960, 2910 (m,sh), 1640 (m,sh), 1410 (m,br), 1250 (s,sh),1132, 1120 (m,sh), 1052 (m,sh), 994 (m,sh), 912 (s,br), 862, 830, 810,775 cm-1(s,br). [m=medium, s=strong, sh=sharp, br=broad].

Mass Spectrum (22.0 V); m/e 378 (M+, 31.8) 363 (50.0), 309 (30.2), 277(24.1), 260 (18.3), 188 (28.8), 176 (53.1), 175 (100.0), 160 (29.2), 135(14.8), 113 (7.8), and 86 (16.7).

High resolution mass spectrometry gave a molecular ion exact massmeasurement of 378.2187 (theoretical: 378,2191).

Analysis. Calculated for C₂₄ H₃₄ Si₂ (378,708): C, 76.12; H, 9.05; Si,14.83. Found: C, 75.26; H, 9.10; Si, 15.64.

Preparation of 2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane:

The compound 2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane,Compound (4) below where n=1, was prepared in accordance with thefollowing reaction. ##STR12##

To a solution of 34.15 g (80% purity, 27.84 g assay, 0.161 mole) of3-chloroperoxybenzoic acid (MCPBA) in 400 ml of dichloromethane wasadded a solution of 28.50 g (0.0754 mole) of2,5-bis(3-allylphenyl)-2,5-dimethyl-2.5-disilahexane, Compound (3),where n=1 , prepared as described in Step B above, in 50 ml ofdichloromethane. The clear solution was heated for 0.5 hr at reflux. Theonset of reaction was marked by the clear solution turning turbid.Precipitation of a white solid ensued. The resulting sludge was stirredfor 18 hr, heated for 1 hr and cooled.

The sludge was diluted with an equal volume of hexane and filtered toremove 3-chlorobenzoic acid residues. (Alternatively, the sludge wasconcentrated and the residue was triturated with hexane.) The hexanefiltrate was extracted with four 125-ml portions of a 0.4M sodiumhydroxide solution. From the alkaline washings after acidification andextraction with dichloromethane, there was recovered a small batch of3-chlorobenzoic acid residues. The total recovered 3-chlorobenzoic acidresidue was 31.6 g, representing a 96.9% material balance.

The organic phase after the washings was dried over magnesium sulfate,filtered, and concentrated to an oil. Further heating at 60° C/1.0 torrfor 4 hr removed volatiles and produced a tan-colored oil. Purificationby distillation was attempted and was found to be difficult.Furthermore, using gel permeation chromatography, the distillate wasfound to contain dimeric products.

The product was shown to be Compound 4 where n=1, by its NMR spectrumwhich revealed perfect integration ratios of the absorptions. Asindicated below, the measured epoxy equivalent of the product was veryclose to the theoretical value.

¹ H NMR (CDCl₃) ⊕ 0.23 (s, 12H, SiCH₃), 0.65 (s, 4H, CH₂ Si(CH₃)₃),2.46-3.30 (3closely spaced m's, 10H, characteristic of H's on epoxide),and 7.33 ppm (bs, 8H, aromatics).

Epoxy equivalent weight:

Measured: 230 gm/(gm mole epoxy)

Theoretical: 205 gm/(gm mole epoxy)

Epoxidation of the second batch of Compound 3, n=1 as described in StepB above was performed as described immediately above. The productCompound 4, n=1 had an NMR spectrum which was superimpossible on that ofthe first batch of Compound 4, n=1. Additional characterization isdescribed below.

¹ H NMR (250 MHz, CDCl₃): δ 0.28 (s, 12H), 0.68 (s, 4H), 2.56, 2.57,2.58, 2.59 (dxd, 2H), 2.78-3.00 (m, 6H), 3.17 (bm, 2H), and 7.26-7.46ppm (complex m, 8H).

¹³ C NMR (62.8 MHz, CDCl₃): δ -3.4, 8.0, 39.0, 47.0, 52.6, 128.0, 129.6,132.1, 134.4, 136.5, and 139.8 ppm.

Mass Spectrum (22.0 V): m/e 410(24), 394(16), 367(20), 337(22), 311(17),161(29), 117(100), 75(83).

High resolution mass spectrometry gave a molecular ion exact massmeasurement of 410.2077 (theoretical: 410.2089).

EXAMPLE 2

This example illustrates the preparation and characterization of curedresins from the2,5-bis-(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane, Compound (4),n=1, prepared as described in Example 1.

The Compound 4 where n=1 prepared as in Example 1 was cured with1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl-1,3-disiloxane (APMD) at 90%stoichiometry. The cure schedule was 14 hours at 66° C. and 2 hours at121° C.

Differential scanning calorimetry (DSC) of the cured resin revealed aglass transition temperature (Tg) of 16° C. with a decompositiontemperature (Td) of 260° C. It is noteworthy that this compound has arelatively low Tg and relatively high Td as compared to commercial epoxymaterials. Further characterization by thermomechanical analysis (TMA)showed a softening temperature around 5° C. Rheometric dynamicmechanical spectroscopy (RDMS) analysis gave a Tg of 32° C., and adynamic storage modulus (G') value of 1.7×10⁷ dynes/cm² (247 psi) for athermally conditioned specimen.

The outgassing results showed a total mass loss (TML) of 2.06% andcollectible volatile condensable material (CVCM) of 0.61%. The outgassedmaterial was found to be unreacted epoxy. These results indicated thatby using the appropriate stoichiometry (i.e., reacting all the epoxy),the outgassing can be brought within NASA requirements. (See Table II,fifth item). The relatively low outgassing properties of this resin areprobably due to the stability of the two-carbon chain between thesilicon atoms. The stable methylene chain does not have the propensityto undergo rearrangement-reversion as the prior art siloxane chain does.Therefore, no undesirable oligomers were found when Compound 4 where n=1was cured. Hydrolytically, the disilethylene chain is expected to bemore stable than the siloxane chain.

Additional batches of the above-noted resin were prepared by curingCompound 4 where n=1 with various amounts of the1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyl-1,3-disiloxane (APMD) curingagent to obtain 90%, 95%, 100%, and 107% stoichiometry, amine to epoxy.The ambient temperature viscosity of the uncured resin was 470centipoise, as determined using a Brookfield viscometer. The cureschedule was 14 hours at 66° C. and 3 hours at 121°C. The cured resinswere clear and ranged from light tan to light brown in color. Thephysical properties ranged from a hard rubber (90% stoichiometry) to astiff but tough plastic (107% stoichiometry). The differential scanningcalorimetry results are summarized in Table I and indicate Tg valuesfrom 10° C. (for the 90% stoichiometry) to 37° C. (for the 110%stoichiometry) and decomposition temperatures (Td's) from 240° C. (forthe 95% stoichiometry) to 340° C. (for the 107% stoichiometry). The highdecomposition temperature of the latter specimen was noteworthy.Commonly used toughened epoxy resins possess much lower decompositiontemperatures (significantly below 300° C.). The low decompositiontemperatures of commercially available compliant epoxies are generallydue to the poor thermal resistance of the commonly employedflexibilizing agents such as polysulfides, digylcidyl esters of linoleicacid dimer, carboxy-terminated butadiene acrylonitrile (CTBN) rubbers,aliphatic polyamides, and amido-polyamides.

Adhesive peel strength testing was carried out with the 90%stoichiometry formulation with a 5 mil bondline. The measured peelstrength of 19 lbs per inch width (piw) indicated that the material hasa high level of toughness. As a comparison, typical peel strength for abrittle material is ≦ 2 piw, and a compliant (rubbery) material willhave typical peel strengths between 10 and 25 piw.

                  TABLE I                                                         ______________________________________                                        DSC RESULTS                                                                   FOR EXAMPLE 2                                                                         Epoxy Equivalent                                                                            Stoichio-                                               Run     Weight        metry                                                   No.     Actual  Theoretical                                                                             (%)    Tg (°C.)                                                                      Td (°C.)                       ______________________________________                                        1       230     205       90     10     280                                                             95     17     240                                                             100    21     290                                                             107    25     340                                                             107.sup.a                                                                            33     335                                   2       272     205       107.sup.a                                                                            28-44  335                                   3       229     205       110.sup.a                                                                            25-37  335                                   ______________________________________                                         .sup.(a) Molecularly distilled at 124° C. Run Nos. 1 and 2, monome     prepared by method of Example 1, first batch. Run No. 3, monomer prepared     by method of Example 1, second batch.                                    

Outgassing experiments performed on the various formulations aresummarized in Table II. The molecularly distilled 107% stoichiometrysample yielded a total mass loss (TML) of 0.64% and a collectiblevolatile condensable material (CVCM) weight of 0.03%. When tested inaccordance with the American Society for Testing Materials (ASTM)specification, the NASA requirement for passing outgassing tests forspace applications is TML ≦ 1.0% and CVCM ≦ 0.10%.

The epoxy resin prepared in accordance with Example 1 and having anepoxy equivalent weight of 272 had a viscosity of 410-420 centipoise anda refractive index of 1.5458 (measured at 24° C.)

                  TABLE II                                                        ______________________________________                                        STOICHIOMETRY STUDY - OUTGASSING DATA                                         FOR EXAMPLE 2                                                                 Epoxy Equivalent                                                              Weight                                                                        Run          Theo-   Stoichio-                                                No.  Actual  retical metry (%)                                                                             TML.sup.(a)                                                                         CVCM.sup.(b)                                                                         WVR.sup.(c)                         ______________________________________                                        1.sup.e                                                                            230     205      90     3.24  0.56   0.1                                                       95     2.67  0.20   0.09                                                     100     2.22  0.05   0.09                                                     107     2.16  0.03   0.08                                                     107.sup.d                                                                             0.64  0.03   0.09                                2    272     205     107.sup.d                                                                             1.58  0.13   0.08                                ______________________________________                                         .sup.(a) Total mass loss                                                      .sup.(b) Collectible volatile condensable materials                           .sup.(c) Water vapor recovery                                                 .sup.(d) Sample was molecularly distilled at 124° C.                   .sup.(e) Run Nos. 1 and 2, monomer prepared by method of Example 1, first     batch.                                                                   

EXAMPLE 3

This example illustrates the preparation of2,5-bis(4-allylphenyl)-2,5-dimethyl-2,5-disilahexane and2,5-bis(4-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane. The proceduredescribed in Example 1 was followed with the exceptions noted below.

A. Preparation of 3(4-bromophenyl) propene:

The procedure described in Example 1, Step A was followed except that1,3-dibromobenzene was replaced by 1,4-dibromobenzene and the productwas 3-(4-bromophenyl) propene having the following formula: ##STR13##The NMR results for this product were as follows: NMR (CDCl₃) δ 3.30(bd, 2H, benzylic H's) 4.92, 5.15 (2bm, 2H, geminal H's), 5.56-6.31 (m,1H, vinyl H), and 7.20 ppm (q, 4H, J=8 Hz, aromatic).

B. Preparation of 2,5-bis(4-allylphenyl)-2,5-dimethyl-2,5-disilahexane:

The procedure described in Example 1, Step B was followed except that3-(4- bromophenyl) propene was substituted for 3-(3-bromophenyl)propene. The product, obtained in 72% yield, was2,5-bis(4-allylphenyl)-2,5-dimethyl-2,5-disilanexane having thefollowing formula: ##STR14## The NMR results for this product were asfollows: NMR (CDCl₃) δ 0.25 (s, 12H, SiCH₃), 0.57 (s, 4H, --CH₂, Si),3.32, 3.43 (2 bs, 4H, --CH₂ --), 4.97, 5.17 (2 bm, 4H, geminal)5.67-6.38 (m,2H, vinyl), and 7.30 ppm (q,8H, J=7H, aromatic).

C. Preparation of2,5-bis(4-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane:

The procedure described in Example 1, Step C was followed except that2,5-bis(4-allylphenyl)-2,5-dimethyl-2,5-disilahexane was substituted for2,5-bis(3-allyphenyl)-2,5-dimethyl)-2,5-disilahexane. The product was2,5-bis(4-glycidiphenyl)-2,5-dimethyl-2,5-disilahexane, Compound 5,having the formula: ##STR15## After the solvents were stripped off, thecrude Compound 5 was further purified by passing down a Kontes designfalling film molecular distillation apparatus at 80° C. and at apressure less than 1×10⁻⁴ torr.

The NMR results for this product were as follows: NMR (CDCl₃) δ 0.23 (s,12H, SiCH₃), 0.65 (s, 4H, CH₂ --Si), 2.46-3.30 (3 m's, 10H,characteristic of H's on epoxide), and 7.30 ppm (distorted q, 8H,aromatic).

EXAMPLE 4

This example illustrates the preparation and characterization of a curedresin from the 2,5-bis-(4-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane,Compound 5 where n=1, prepared as described in Example 3.

The Compound 5, n=1 prepared as in Example 3 was cured with1,3-bis(aminopropyl)-1,1,3,3-tetramethyl-1,3-disiloxane (APMD) at 100%stoichiometry. The cure schedule was 16 hours at 71° C. and 2 hours at121° C.

DSC of the cured resin revealed a Tg of 40° C. with a Td of 340° C. TMAdeterminations gave a Tg of 56° C.

These results indicate that the cured resin formed from the para isomeris more thermally stable and has a higher Tg than the cured resin fromthe meta isomer of Example 2. This result is expected from thewell-established general structure-property relationship of meta andpara catenations of polymer chains.

The outgassing results showed a TML of 1.45 % and a CVCM of 0.10%.

EXAMPLE 5

This example illustrates the preparation ofα,α'-bis[(3-allylphenyl)dimethylsilyl]-1,4-xylene andα,α'-bis[(3-glycidylphenyl)dimethylsilyl]-1,4-xylene.

The procedure described in Example 1 is followed except that in Step B,Compound (2) is replaced by α,α'-bis(chlorodimethylsilyl)-1,4-xylene andthe product formed has the formula: ##STR16## Epoxidation of theabove-noted compound as described in Step C of Example 1 produces theproduct having the formula: ##STR17##

EXAMPLE 6

This example illustrates the preparation of2,11-bis(3-allylphenyl)-2,11-dimethyl-2,11-disiladodecane [Compound 3,n=4], and 2,11-bis(3-glycidylphenyl)-2,11-dimethyl-2,11-disiladodecane[Compound 4, n=4]in accordance with the present invention.

A. Preparation of 3-(3-bromophenyl)propene:

3-(3-bromophenyl)propene was prepared as described in Example 1, Step A.

B. Preparation of2,11-bis(3-allylphenyl)-2,11-dimethyl-2,11-disiladodecane:

The compound 2,11-bis(3-allylphenyl)-2,11-dimethyl-2,11-disiladodecane,also named 1,8-bis(3-allylphenyl-dimethylsilyl)octane [Compound 3, wheren=4] was prepared in accordance with the reaction shown in Example 1,Step B.

To a flame dried 2-liter 3-neck flask fitted with a reflux condenser anda dropping funnel there was added 13.00 g of magnesium turnings (0.5350moles) and 200 ml of anhydrous tetrahydrofuran (THF), freshly distilledfrom sodium. To this mixture was added, via the addition funnel, 10 mlof a solution of 102.27 g (0.5194 moles) of 3-(3-bromophenyl) propene in200 ml of anhydrous THF.

Following initiation of the reaction, the remainder of the3-(3-bromophenyl)propene solution was added dropwise at such a rate asto maintain a gentle reflux. After complete addition, the solution washeated at reflux for 1 hour.

A solution of 70.0 g (0.2337 moles) of2,11-dichloro-2,11-dimethyl-2,11-disiladodecane, available commerciallyfrom Petrarch Systems as 1,8-bis(chlorodimethylsilyl)octane, in 150 mlof anhydrous THF was transferred to the now empty addition funnel andadded to the reaction mixture, still under reflux. After completeaddition, the reaction was heated at reflux for 1-2 hours, cooled andallowed to stir at room temperature overnight.

Work-up was accomplished by pouring the reaction mixture into 800 ml ofa cold, saturated ammonium chloride solution. The aqueous layer wasseparated and extracted with three 300-ml portions of ether. Thecombined organic fractions were washed once with aqueous ammoniumchloride, once with water, and finally dried over magnesium sulfate.

After the solvents were removed on a rotary evaporation, the crudeproduct was further purified by passing down a Kontes design fallingfilm molecular distillation apparatus at a pressure less than 1×10⁻⁴torr using refluxing water as the external heating fluid. The yield ofthe purified product was 86.70 g (80.3%). Characterization data obtainedby NMR spectrometry are as follows. ¹ H NMR (CDCl₃) δ 0.1 (s, 12H,SiCH₃), 0.45 (bm, 4H, SiCH₂ --), 1.0 (bm, 12H, --CH₂ --), 3.1 (bd, 4H,benzylic H's), 4.8 (bd, 4H, terminal vinyl H's), 5.7 (bm, 2H, vinyl H),and 7.1 ppm (bm, 8H, aromatic).

C. Preparation of2,11-bis(3-glycidylphenyl)-2,11-dimethyl-2,11-disiladodecane:

The compound2,11-bis(3-glycidylphenyl)-2,11-dimethyl-2,11-disiladodecane (Compound4, where n=4), was prepared in accordance with the reaction shown inExample 1, Step C.

To a 2-liter 3-neck flask equipped with a dropping funnel, mechanicalstirrer and reflux condenser was added 85.01 g of 3-chloroperoxybenzoicacid (85% assay) and 450 ml of dichloromethane. The partial solution washeated to reflux, upon which complete solubility was obtained.

To this solution was added at reflux a solution of 86.70 g (0.1877moles) of 2,11-bis(3-allylphenyl)-2,1-dimethyl-2,11-disiladodecane,Compound 3 where n=4, prepared in Step B above, in 100 ml ofdichloromethane. Following complete addition, the reaction mixture waskept at reflux for 15 hours, during which a copious amount of whiteprecipitate formed. The solution was cooled and filtered. The filtratewas concentrated to an oil, resulting in further precipitation. Thecrude product was filtered, dissolved in 500 ml of hexane, washed withthree 100-ml portions of aqueous sodium hydroxide, followed by anaqueous ammonium chloride wash and a final water wash. The hexanesolution was dried over magnesium sulfate, filtered, and concentrated.

Final purification of the crude2,11-bis(3-glycidylphenyl)-2,11-dimethyl-2,11-disiladodecane wasaccomplished by passing it down a Kontes design falling film moleculardistillation apparatus at a pressure less than 1×10⁻⁴ torr usingrefluxing butyl acetate as the external heating fluid. Residual solventand other volatiles were removed. The final product was characterized byNMR spectrometry as follows. ¹ H NMR (CDCl₃) δ 0.1 (s, 12H, SiCH₃), 0.45(bm, 4H, SiCH₂), 1.0 (bm, 12H, --CH₂ --), 2.0-3.9 (overlapping m's, 10H,characteristic of epoxide ring), and 6.8-7.4 ppm (m, 8H, aromatic).

EXAMPLE 7

This example illustrates an alternative method for the preparation of2,11-bis(3-allylphenyl)-2,11-dimethyl-2,11-disiladodecane (Compound 3,n=4) using an inverse addition mode for the Grignard reaction.

To a flame dried 2-liter 3-neck flask fitted with a mechanical stirrer,reflux condenser, and an addition funnel was added 70.19 g (2.887 moles)magnesium turnings and 500 ml of anhydrous tetrahydrofuran (THF).

A solution consisting of 541.6 g (2.751 moles) of3-(3-bromophenyl)propene, prepared as in Example 1, Step A, in 150 mlanhydrous THF was placed into the addition funnel. An aliquot of thissolution was added to the reaction flask. Reaction initiated immediatelyand addition was continued dropwise at such a rate as to maintain agentle reflux. Following complete addition the reaction was heated atreflux for 3 hours.

The addition funnel was replaced with a rubber septum and the reactionmixture transferred via cannulation to a 5-liter flask containing 392.34g (1.310 moles) of 2,11-dichloro-2,11-dimethyl-2,11-disiladodecane in 1liter refluxing THF. In a first batch, both flasks were kept at refluxtemperature throughout the addition. (In a second batch, both flaskswere kept at ambient temperature throughout the addition.) Followingcomplete addition, the reaction was heated an additional half hour atreflux, cooled to room temperature and allowed to stir 16 hours.

Work-up was accomplished by pouring the reaction mixture into 3 litersof cold, saturated aqueous ammonium chloride and extracting with three750-ml portions of hexane. The combined organic fractions were washedwith water and dried over magnesium sulfate. Following solvent removal,final purification was accomplished by passing the crude oil down afalling film molecular distillation apparatus at a pressure less than10⁻⁴ torr using refluxing water as the heating fluid. The yield was578.1 g (95.52%) for the first batch and 72.3% for the second batch.

Characterization of the2,11-bis(3-allylphenyl)-2,11-dimethyl-2,11-disiladodecane reactionproduct formed by this alternative method was accomplished by spectralcomparison with the product of Example 6, Step B.

The above-noted bis-allyl product was epoxidized with3-chloroperoxybenzoic acid and the epoxy product, Compound 4, n=4, waspurified by passage from a falling film molecular distillation apparatustwice at a pressure less than 10⁻⁴ torr using refluxing butyl acetate(125° C.) as the external heating fluid, as described in Example 6, StepC.

A third batch of Compound 3, n=4 was prepared as described above for thefirst batch, and subsequently epoxidized to produce Compound 4, n=4.Both Compound 3, n=4 and Compound 4, n=4 obtained from this third batchrun were fully characterized by the methods and data given below.

For Compound 3, n=4,

¹ H NMR (250 MHz, CDCl₃): δ 0.29 (s, 12H), 0.74-0.81 (bm, 4H), 1.26-1.34(m, 12H), 3.42 (d, 4H, J=6.6 Hz), 5.08 (bs, 2H), 5.11-5.16 (d, 2H, J=8.9Hz), 5.93-6.09 (complex m, 2H), and 7.18-7.40 ppm (complex m, 8H).

¹³ C NMR (62.8 MHz, CDCl₃): δ -2.7, 15.9, 24.1, 29.4, 33.8, 40.5, 115.9,128.0, 129.2, 131.5, 133.9, 137.7, 139.3, and 140.0 ppm.

Refractive index measured at 24° C.: 1,5223.

IR (film) 2920 (s, sh), 1640 (m,sh), 1410 (s,br), 1250 (s,sh), 1120(s,sh), 992 (m,sh), 912 (s,br), 865, 835, 810, 780 (s,br), and 710 cm⁻¹(s,br).

Mass Spectrum (22.0 V): m/e 462 (m+, not observed), 344 (36.0), 257(22.2), and 175 (100.0)

High resolution mass spectrometry gave a molecular ion exact massmeasurement of 462.3135 (theoretical: 462.3130).

Analysis. Calculated for C₃₀ H₄₆ Si₂ (462.870): C, 77.85; H, 10.02; Si,12.13. Found: C, 77.54; H, 10.31; Si, 12.15.

For Compound 4, n=4

¹ H NMR (250 MHz, CDCl₃); δ 0.26 (s, 12H), 0.71-0.77 (bm, 4H), 1.24-1.29(bm, 12H), 2.56, 2.57, 2.58, 2.59 (dxd, 2H, J's=5.0, 2.6, Hz), 2.79-2.85(m, 4H), 2.90, 2.93, 2.96, 2.99 (dxd, 2H, J's=14.4, 5.6 Hz), 3.14-3.20(bm, 2H), and 7.24-7.41 ppm (complex m, 8H).

¹³ C NMR (62.8 MHz, CDCl₃): δ -2.8, 15.9, 24.0, 29.4, 33.8, 39.1, 47.0,52.7, 128.1, 129.6, 132.1, 134.3, 136.5, and 140.3 ppm.

Mass Spectrum (22.0 V): m/e 494 (M+, not observed), 361 (20), 271 (12),161 (34), 117 (100), and 75 (78).

High resolution mass spectrometry gave a molecular ion exact measurementof 494.3026 (theoretical: 494.3028).

Epoxy equivalent weight:

measured, 267 gm/gm-mole epoxy

theoretical, 247 gm/-mole epoxy

EXAMPLE 8

This example illustrates the characterization of cured resins of2,11-bis(3-glycidylphenyl)-2,11-dimethyl-2,11-disiladodecane prepared asdescribed in Examples 6 and 7. The viscosity for the uncured epoxy resinprepared as described in Example 7 was 350-356 centipoise. These resinswere cured with 1,3-bis(aminopropyl)-1,1,3,3-tetramethyl-1,3-disiloxane(APMD) at the stoichiometries indicated in Table III for 16 hours at160° F. (71° C.) and post-cured for 4 hours at 250° F. (121° C.). TheTg, Td, and outgassing values measured for the cured resins are shown inTable III. It was noted that the method of Example 7 using inverseaddition at reflux resulted in a monomer having a lower epoxy equivalentweight and a cured product having lower outgassing values than themethod of Example 7 using inverse addition at ambient temperature.

                                      TABLE III                                   __________________________________________________________________________    PROPERTIES OF CURED RESINS                                                    (EXAMPLE 8)                                                                          Epoxy                                                                         Equivalent                 (1)                                                Weight (eew)                                                                            Stoichiometry                                                                        Tg (°C.)                                                                      Td Outgassing (%)                              Material                                                                             Actual                                                                            Theoretical                                                                         (%)    TMA DSC                                                                              (°C.)                                                                     TML CVCM                                                                              WVR                                 __________________________________________________________________________    Example 6                                                                            321 247   100    3   -2 335                                                                              0.91                                                                              0.11                                                                              0.11                                                 107    20  1  325                                                                              1.10                                                                              0.12                                                                              0.12                                                 115    37  0  315                                                                              1.18                                                                              0.15                                                                              0.15                                                 90     12  -4 305                                                                              0.86                                                                              0.14                                                                              0.10                                Example 7,                                                                           290 247   90     --  -- -- 1.85                                                                              0.46                                                                              0.13                                Batch 2          100    14  -2 345                                                                              1.14                                                                              0.17                                                                              0.09                                (Inverse         110    16  5  325                                                                              1.33                                                                              0.10                                                                              0.08                                Addition at                                                                   ambient                                                                       temperature)                                                                  Example 7                                                                            275 247   90     --  -- -- 1.47                                                                              0.45                                                                              0.09                                Batch 1          100    22  5  300                                                                              0.88                                                                              0.14                                                                              0.10                                (Inverse         110    20  8  335                                                                              1.03                                                                              0.07                                                                              0.09                                Addition at                       (2)                                         reflux)                                                                       Example 7                                                                            267 247   110    --  0-15                                                                             335                                                                              --  --  --                                  Batch 3                                                                       (Inverse                                                                      Addition at                                                                   reflux)                                                                       __________________________________________________________________________     (1) TML = total mass loss CVCM = collectable volatile condensable             materials WVR = water vapor recovered                                         (2) Standard practice allows adjustment of TML values that are slightly       greater than 1.0. The adjustment is to subtract the WVR value. The            adjusted TML value = 1.03 - 0.09 = 0.94 percent.                         

EXAMPLE 9

This example illustrates the further characterization of cured resins of2,11-bis(3-glycidylphenyl)-2,11-dimethyl-2,11-disiladodecane prepared asdescribed in Example 7 and cured with various hardeners. The resin wascured with the hardeners and at the stoichiometries indicated in TableIV. Table IV shows the properties of the cured resins. Table V presentsadditional mechanical, electrical, and physical properties of the curedepoxy resin formed from the compound prepared as described in Example 7using 110% stoichiometry of the1,3-bis(aminobutyl)-1,1,3,3-tetramethyl-1,3-disiloxane (ABMD) hardener(Table IV, item 6).

                                      TABLE IV                                    __________________________________________________________________________    PROPERTIES OF RESINS CURED WITH VARIOUS HARDENERS                             (EXAMPLE 9)                                                                   Stoichiometry    Tg (°C.)                                                                       Td   Outgassing                                      Item                                                                             (%)    Hardener                                                                             TMA DSC (°C.)                                                                       TML CVCM                                                                              WVR                                     __________________________________________________________________________    1  90     APMD   --  -8  255  1.19                                                                              0.42                                                                              0.12                                    2  100    APMD   --  0   315  0.81                                                                              0.15                                                                              0.10                                    3  110    APMD   21  2   320  0.98                                                                              0.2 0.11                                    4  90     ABMD   --  -11 270  1.21                                                                              0.37                                                                              0.11                                    5  100    ABMD   --  -5  320  0.95                                                                              0.30                                                                              0.12                                    6  110    ABMD   10  4   310  0.98                                                                              0.08                                                                              0.11                                    7  90     TETA   -16 --  210  --  --  --                                      8  100    TETA   20-40                                                                             15  210  --  --  --                                      9  90     NMA/2,4EMI                                                                           65  43  175-177                                                                            --  --  --                                      10 100    NMA/2,4EMI                                                                           50-74                                                                             43-52                                                                             167-188                                                                            --  --  --                                      __________________________________________________________________________     APMD = 1,3bis(3-aminopropyl)-1,1,3,3-tetramethyl-1,3-disiloxane               ABMD = 1,3bis(3-aminobutyl)-1,1,3,3-tetramethyl-1,3-disiloxane                TETA = triethylenetetraamine                                                  NMA = nadic methylanhydride, stoichiometry based on anhydride 2,4EMI =        2ethyl-4-methylimidazole                                                 

                  TABLE V                                                         ______________________________________                                        MECHANICAL, ELECTRICAL, AND PHYSICAL                                          PROPERTIES OF CURED RESIN                                                     (EXAMPLE 9)                                                                   Property                Values                                                ______________________________________                                        Monomer epoxy equivalent weight, g                                            Actual                  357                                                   Theoretical             247                                                   Uncured resin viscosity at                                                                            528                                                   room temperature, cps                                                         Glass transition temperature, °C.                                                              4-10                                                  Decomposition temperature, °C.                                                                 310                                                   Outgassing                                                                    Total mass loss, %      0.98                                                  Collectable volatile condensible                                                                      0.08                                                  materials, %                                                                  Water vapor recovery, % 0.11                                                  Specific gravity        1.11                                                  T-peel strength, kg per cm width                                                                      1.7                                                   (lb per in width)       (9.4)                                                 Elongation, %           83                                                    Tensile strength, MPa (psi)                                                                           2.3 (330)                                             Lapshear strength, MPa (psi)                                                                          2.7 (400)                                             Dielectric constant at 1 kHz                                                                          3.45                                                  Dissipation Factor at 1 kHz                                                                           0.087                                                 Volume Resistivity, Ω-cm                                                                        4.4 × 10.sup.15                                 Dielectric strength, volts/mm                                                                         4.06 × 10.sup.5                                 (volts/mil)             (1.03 × 10.sup.3)                               ______________________________________                                    

EXAMPLE 10

This example illustrates the preparation of2,9-bis(3-allylphenyl)-2,9-dimethyl-2,9-disiladecane and2,9-bis(3-glycidylphenyl)-2,9-dimethyl-2,9-disiladecane. The procedure(using the normal addition mode) described in Example 6 was followedexcept that in Step B, Compound 2 where n=4 was replaced with Compound 2where n=3, and the product formed was Compound 3 where n=3. In Step C,the product formed was Compound 4 where n=3.

The purified product yield for Compound 3 (n=3) was 81.2% and thepurified product yield for Compound 4 (n=3) was 80.2%. Compounds 3 and 4(n=3) were characterized by their respective NMR spectra.

Compound 3 (n=3):

NMR (CDCl₃) δ 0.1 (s, 12H, SiCH₃), 0.5 (bm, 4H, --SiCH₂ --), 1.1 (bm,8H, --CH₂ --), 3.1 (bd, 4H, benzylic H's), 4.8 (bm, 4H, terminal vinylH's), 5.35-6.05 (bm, 2H, vinyl H's), and 6.7-7.4 ppm (m, 8H, aromatic).

Compound 4 (n=3):

NMR (CDCl₃) δ 0.1 (s, 12H, SiCH₃), 0.5 (bm, 4H, --SiCH₂ --), 1.1 (bm,8H, --CH₂ --), 2.1-3.0 (overlapping m's, 10H, characteristic of anepoxide ring), and 6.9-7.4 ppm (m, 8H, aromatic).

The viscosity of Compound 4, n=3 was determined to be 245-250centipoise.

EXAMPLE 11

This example illustrates an alternative method (the Barbier method) forthe preparation of 2,9-bis-(3-allylphenyl)-2,9-dimethyl-2,9-disiladecane(Compound 3, n=3) and2,9-bis(3-glycidylphenyl)-2,9-dimethyl-2,9-disiladecane (Compound 4,n=3). In the Barbier variation of the Grignard reaction, theorganomagnesium reagent is formed in situ in the presence of theelectrophile in order to maintain a low concentration of the reagent andthus minimize side reactions. (By contrast in the classic Grignardreaction, the organomagnesium reagent is first formed from R-Br,followed by addition of the electrophile.)

To a flame dried 500 ml 3-neck flask equipped with a magnetic stirrer,reflux condenser, and dropping funnel there was added 9.41 g of drymagnesium (0.3869 moles), 50.00 g of2,9-dichloro-2,9-dimethyl-2,9-disiladecane (0.1842 moles), and 150 mlanhydrous tetrahydrofuran.

Five ml of a solution of 76.17 g of 3-(3-bromophenyl)propene, preparedas in Example 1, Step A, (0.3869 moles) in 100 ml anhydroustetrahydrofuran was added by means of the addition funnel. Reactioninitiated immediately and addition of the 3-(3-bromophenyl)propene wascontinued at a rate to maintain a gentle reflux. Following completeaddition, the reaction was heated at reflux for 2 hours, and then cooledto room temperature.

Work-up of the crude product was accomplished by pouring the reactionmixture into 250 ml of a cold, saturated aqueous ammonium chloridesolution. The aqueous layer was separated, extracted three times with100 ml portions of ether. The combined organic fractions were washedonce with aqueous ammonium chloride, once with water and dried overmagnesium sulfate.

Following solvent removal, the crude oil was purified by passage down afalling film molecular distillation apparatus at a pressure less than1×10⁻⁴ torr using refluxing butyl acetate as the external heating fluid.The resultant product was identified to be2,9-bis-(3-allylphenyl)-2,9-dimethyl-2,9-disiladecane by comparing itsNMR spectrum with that of the product of Example 10, Compound 3 wheren=3.

Epoxidation was accomplished using 3-chloroperoxybenzoic acid to form2,9-bis(3-glycidylphenyl)-2,9-disilodecane, Compound 4, n=3. To a2-liter 3-neck flask equipped with a mechanical stirrer, refluxcondenser and an addition funnel was added 56.54 g of3-chloroperoxybenzoic acid (85% assay) and 200 ml of dichloromethane.This solution was heated to reflux and a solution of 55.16 g (0.1271moles) of 2,9-bis-(3-allylphenyl)-2,9-dimethyl-2,9-disiladecane in 100ml of dichloromethane was added dropwise. The reaction was kept atreflux for 16 hours during which a copious amount of 3-chlorobenzoicacid precipitated. The reaction was next cooled to room temperature,filtered, and the solids were washed with hexane. The solvents wereremoved on the rotary evaporator, at which time additional3-chlorobenzoic acid precipitated. The oil was again filtered, and theprecipitate was washed with hexane. The filtrate was washed four timeswith 5 percent sodium hydroxide, once with saturated aqueous ammoniumchloride and once with water. After drying over magnesium sulfate andfiltering, the solution was concentrated and the oil was then purifiedby passage twice down a falling film molecular distillation apparatus ata pressure less than 10⁻⁴ torr using refluxing butyl acetate (125° C.)as the external heating fluid.

The resultant product was identified to be2,9-bis(3-glycidylphenyl)-2,9-dimethyl-2,9-disiladecane by comparing itsNMR spectrum with that of the product of Example 10, Compound 4, n=3.

EXAMPLE 12

This example illustrates the preparation of2,9-bis(3-allylphenyl)-2,9-dimethyl-2,9-disiladecane, Compound 3, n=3,and subsequent conversion to2,9-bis(3-glycidylphenyl)-2,9-dimethyl-2,9-disiladecane, Compound 4,n=3. The inverse addition procedure described in Example 7 for batch 1was followed except that2,11-dichloro-2,11-dimethyl-2,11-disiladodecane, Compound 2, n=4, wasreplaced with 2,9-dichloro-2,9-dimethyl-2,9-disiladecane, Compound 2,n=3, which was distilled prior to use. The product at this stage wasCompound 3, n=3, whose characterization data are as follows:

¹ H NMR (250 MHz, CDCl₃): δ 0.24 (s, 12H), 0.72 (m, 4H), 1.30 (bs, 8H),3.36 (d, 4H, J=6.6 Hz), 5.03 (bs, 2H), 5.08 (d, 2H, J=8.1 Hz), 5.88-6.01(m, 2H), and 7.13-7.35 ppm (Complex m, 8H).

¹³ C NMR (62.8 MHz, CDCl₃): δ -26, 16.1, 24.1, 33.5, 40.7, 116.0, 128.1,129.4, 131.7, 134.1, 137.9, 139.4, and 140.1 ppm.

Refractive index measured at 24° C.: 1.5243.

IR (film) 2920 (s,sh), 1640 (m,sh), 1410 (s,br), 1250 (s,sh) 1120(s,sh), 992 (m,sh), 910 (s,br), 860, 835, 810, 775 (s,br) 710 cm⁻¹(m,sh).

Mass spectrum (22.0 V) m/e 434 (M+, not observed), 316 (59.2), 277(51.8), 229 (50.0), 198 (41.3), 176 (96.3), 175 (100.0), 140 (25.2), 135(38.4), 127 (49.1), 126 (74.8), and 98 (21.3).

High resolution mass spectrometry gave a molecular ion exact massmeasurement of 434.2809 (theoretical: 434.2817).

The above-noted bis-allyl Compound 3, n=3, was epoxidized in the exactmanner as described in Example 7 for Compound 3, n=4. The product afterthe epoxidation in this case was Compound 4, n=3. Characterization datafor Compound 4, n=3 are as follows:

¹ H NMR (250 MHz, CDCl₃): δ 0.26 (s,12H), 0.73 (bm,4H), 1.30 (bs,8H),2.56, 2.57, 2.58, 2.59, (dxd, 2H, J's=5.0, 2.6 Hz), 2.79, 2.81, 2.83,2.85 (m, 4H), 2.91, 2.93, 2.96, 2.99 (dxd, 2H, J's=14.4, 5.6 Hz),3.14-3.20 (bm, 2H), and 7.24-7.41 ppm (complex m, 8H).

¹³ C NMR (62.8 MHz, CDCl₃): δ -2.9. 15.8, 23.9, 33.3, 39.1, 47.0, 52.6,128.0, 129.5, 132.0, 134.2, 136.5, and 140.2 ppm.

Mass spectrum (22.0 V): m/e 466 (M+, not observed), 191 (6.3), 175(4.5), 161 (33.9), 135 (16.6), 117 (58.8), and 75 (100.0).

High resolution mass spectrometry gave a molecular ion exact massmeasurement of 466.2693 (theoretical 466.2715).

EXAMPLE 13

This example illustrates the characterization of cured resins of2.9-bis(3-glycidylphenyl)-2,9-dimethyl-2,9-disiladecane. Using thecompounds prepared in Examples 10, 11 and 12, test specimens wereprepared at various APMD stoichiometries for thermal and outgasstesting. The results are summarized in Table VI. For the epoxy resinsfrom Examples 10 and 11, the epoxy equivalent weights (eew's) wererespectively, 18% and 29% higher than and the Tg and Td were comparableto those of the resin from Example 12. However, for the cured resin fromthe compound of Example 11, the out-gassing was significantly improved(a reduction of 17% and 72% in TML and CVCM, respectively, for the 102%APMD stoichiometry) over that of the cured resin from Example 10 using100% APMD stoichiometry. These results indicate that in using thesynthesis technique of Example 11, the attainment of near-theoreticaleew may not be critical for meeting the NASA outgassing requirements(≦1.0% TML and ≦0.10 CVCM).

                                      TABLE VI                                    __________________________________________________________________________    PROPERTIES OF CURED RESINS                                                    (EXAMPLE 13)                                                                  Monomer                                                                       Epoxy                                                                         Equivalent                                                                    Weight (eew)    Stoichiometry                                                                        Tg (°C.)                                                                       Td Outgassing (%)                              Material                                                                            Actual                                                                            Theoretical                                                                         (%)    TMA DSC (°C.)                                                                     TML CVCM                                                                              WVR                                 __________________________________________________________________________    Example 10                                                                          304 233   90     --  --  -- 1.71                                                                              0.42                                                                              0.10                                                100    21  0   360                                                                              1.54                                                                              0.46                                                                              0.10                                                107    6   6   335                                                                              1.65                                                                              0.42                                                                              0.10                                                115    19  4   345                                                                              0.83                                                                              0.40                                                                              0.11                                Example 11                                                                          331 233   91     -1  --  250                                                                              --  --  --                                                  102    18  --  325                                                                              1.28                                                                              0.13                                                                              0.07                                                112    16  --  325                                                                              1.44                                                                              0.16                                                                              0.07                                Example 12                                                                          258 233   110    --  -10 to                                                                            340                                                                              --  --  --                                                             +18                                                __________________________________________________________________________

EXAMPLE 14

This example illustrates the use of2,5-bis(3-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane, Compound 4,n=1, prepared as described in Example 1, as a flexibilizer for epoxyresins. Sample A was prepared by mixing Compound 4, n=1 with 50% weightEpon 828. Sample B was prepared by mixing Compound 4, n=1 with 50% byweight of a 50:50 mixture of Glyamine 125 and Glyamine 135. The mixtureswere cured with APMD for 16 hours at 160° F. (71° C.) and post-cured 4hours at 250° F. (121° C.). Samples of Epon 828 alone and the Glyaminemixture alone were similarly cured for comparison. The thermomechanicaldata of the resulting cured resins in shown in Table VII. For Sample A,a 55% increase in T-peel with a decrease in Tg was obtained as comparedto Epon 828 alone. For Sample B, a 740% increase in T-peel was obtainedwith a decrease in Tg as compared to the brittle Glyamine mixture alone.Thus, this compound in accordance with the present invention acts as aflexibilizer. It is expected that the use of the meta isomers ofCompound 4, where n=3 or n=4 as flexibilizers in accordance with thepresent invention will provide further increases in flexibility in theresulting epoxy mixtures as compared to those described above.

                  TABLE VII                                                       ______________________________________                                        FLEXIBILIZING EFFECTS                                                         (EXAMPLE 14)                                                                          Tg (°C.)                                                       Sample    DSC      TMA     Td (°C.)                                                                        T peel (piw)                              ______________________________________                                        A         34       43      250      8.7                                       Epon 828  72       93      280      5.6                                       B         27       42      190      4.2                                       Glyamine  45       62      250      0.5                                       Mixture                                                                       ______________________________________                                         Epon 828 is a diglycidyl ether of bisphenol A, from Shell Chemicals           Glyamine mixture comprises 50:50 glyamine 125 and glyamine 135                (diglycidylaniline and diglycidylorthotoluidine, from FIC Resins Division                                                                              

EXAMPLE 15

This example illustrates the use of2,5-bis(4-glycidylphenyl)-2,5-dimethyl-2,5-disilahexane, Compound 4,n=1, prepared as described in Example 3, as a toughener for epoxyresins. Sample A was prepared by mixing Compound 4, n=1, with 50% byweight of a 50:50 mixture of Glyamine 125 and Glyamine 135. Sample B wasprepared by mixing Compound 4, n=1, with 70% by weight of a 50:50mixture of Glyamine 125 and Glyamine 135. The mixtures were cured withAPMD for 16 hours at 160° F. (71° C.) and post-cured 4 hours at 250° F.(121° C.). Samples of the Glyamine mixture alone were similarly curedfor comparison. The thermomechanical data of the resulting cured resinsis shown in Table VIII. For Samples A and B, increases of 65% and 103%,respectively, in T-peel with no significant loss in Tg were obtained.Thus, the para compounds of the present invention act as tougheners. Itis expected that the use of para isomers of Compound 4 where n=3 and n=4as tougheners in accordance with the present invention will providefurther increases in toughness in the resulting epoxy mixtures ascompared to those described above.

                  TABLE VIII                                                      ______________________________________                                        TOUGHENING EFFECTS                                                            (EXAMPLE 15)                                                                             Tg (°C.)                                                                             Td     T peel                                        Sample     via DSC       (°C.)                                                                         (piw)                                         ______________________________________                                        A          38            290    1.0                                           B          42            300    1.2                                           Glyamine   45            295    0.6                                           mixture                                                                       ______________________________________                                         Glyamine mixture  see note to Table VII.                                 

EXAMPLE 16

This example illustrates the characterization of cured resins of thebisallyl compound 2,5-bis(3-allylphenyl)-2,5-dimethyl-2,5-disilahexane,Compound 3, n=1, and2,11-bis(3-allylphenyl)-2,11-dimethyl-2,11-disiladodecane, Compound 3,n=4, as prepared in Examples 1 and 6, respectively.

The Compound 3, n=1, and Compound 3, n=4 were each cured byhydrosilation as follows. The platinum catalyst was prepared bydissolving 31 mg of chloroplatinic acid into approximately 2 ml of octylalcohol. The hardener used was PS121 polymethylhydrosiloxane (2-5centistoke viscosity), obtained from Petrarch Chemicals. Two grams ofCompound 3, n=1 were combined with 1.8 g of PS121 and 4 drops ofplatinum catalyst, and mixed for two minutes. The resulting clear,water-white solution was cured overnight at ambient temperature. Theresulting cured specimen was solid, clear, and friable.

Two grams of Compound 3, n=4, were combined with 0.7 g of PS121 and 4drops of platinum catalyst and mixed for 2 minutes. This gave a cloudysolution which was cured for 1 hour at 100° C., followed by 1 hour at125° C. The resulting cured specimen was solid, black, and friable.

The DSC results of the cured material obtained from Compound 3, n=1, andCompound 3, n=4, are summarized in Table IX. This data shows that lowerTg's can be obtained from copolymers of the Compound 3 where n=4 thanfrom those of Compound 3 where n=1 with the maintenance of good thermalstability for both species. These results are consistent with thoseobtained from curing studies performed on Compound 4, n=1, and Compound4, n=4 as described, respectively, in Example 2 and in Examples 8 and 9.

                  TABLE IX                                                        ______________________________________                                        DSC RESULTS OF CURED BISALLYL COMPOUNDS                                       (EXAMPLE 16)                                                                  Material       Tg (°C.)                                                                          Td (°C.)                                     ______________________________________                                        Compound 3     -50 to -30 295                                                 n = 1                                                                         Compound 3     -75 to -50 325                                                 n = 4                                                                         ______________________________________                                    

EXAMPLE 17

This example illustrates the use of2,11-bis(3-glycidylphenyl)-2,11-dimethyl-2,11-disiladodecene, Compound4, n=4, as protective coatings for composite structures.

Two 12-ply, 12 inch×12 inch laminates were fabricated using a[90/0/±45/0/90] orientation of unidirectional graphite prepreg ofFiberite 934 (from Fiberite Corp.) on Hysol/Grafil HMS high strength,medium modulus fiber (from Hysol/Grafil Co.). During the prepreg layup,a peel ply was placed on the top ply only. The prepreg layup was presscured as follows: (1) the layup was vacuum bagged and placed in a 250°F. (121° C.) for press for 15 minutes under a minimum vacuum of 27inches Hg; (2) the bag vacuum was released and 100 psi was applied tothe layup for 45 minutes at 250° F. (121° C.); (3) the layup was ramped2°-6° F./ minute (1°-3° C./minute) to 355° F. (179° C.); (4) the layupwas cured for 355° F. (179° C.) for two hours. Immediately prior tocoating, the peel ply was removed and half of the front surface of eachpanel was lightly sanded with 320 grit paper, followed by 500 gritpaper. The sanded half of panel A was coated to a dry film thickness of0.001 inch (0.0254 mm) with Compound 4, n=4, as prepared in Example 7,batch 3 (267 eew), which had been mixed with 100% stoichiometry oftriethylenetetraamine. The sanded half of panel B was coated to a dryfilm thickness of 0.005 inches (0.0127 mm) using Compound 4, n=4, halfof which was prepared as in Example 7, batch 3 (267 eew), and half ofwhich was prepared by the process of Example 7 except as modified by theBarbier technique (360 eew).Each batch of resin on panel B was mixedwith 100% stoichiometry of triethylenetetraamine and applied as discretelayers. Both panels were cured at 250° F. for three days.

After cure of Compound 4, n=4, the entire surfaces of both panels wereimmediately coated to a dry film thickness of 0.0006 to 0.0009 inches(0.0152-0.0229 mm) with epoxy primer conforming to MIL-P-23377, PrimerCoatings; Epoxy-Polyamide, Chemical and Solvent Resistant. The primedpanels were dried one-half hour at ambient temperature, followed by a2-hour bake at 199° F. (93° C.). The panels were then topcoated to a dryfilm thickness of 0.0017 to 0.0023 inches (0.0432-0.0584 mm) withpolyurethane paint conforming to MIL-C-83286B. Coating, Urethane,Aliphatic Isocyanate, For Aerospace Applications. The panels were curedfor seven days at ambient conditions, followed by 96 hours at 210° F.(98.9° C.). Thus, the protected half of each panel comprises a graphitecomposite laminate, an interlayer of the polymer of the compound of thepresent invention, a primer layer, and a polyurethane paint layer. Theunprotected half of each panel comprises a graphite composite laminate,a primer layer, and a polyurethane paint layer.

Both panels were then subjected to plastic bead blast,using abrasiveblasting machines equipped with Polyextra 20/30 Type AGO plastic beadmedia, manufactured by U.S. Plastics and Chemical Co. The blast nozzlepressure was 70 psi (0.5 megapascals). The pellet blasts were directedat the center of each panel to simultaneously remove the paint on theunprotected half of the panel and on the half of the panel protectedwith the polymer of Compound 4, n=4 as an interlayer.

For Panel A, it was found that the interlayer of the polymer of Compound4, n=4 was still intact after complete paint and primer removal from a2.18 inch (55.4 mm) area. By contrast, one ply of the graphite compositematerial on the unprotected side in a 2.25 inch (57.2 mm) area had beenpenetrated, leaving several depressions, the largest of which was 0.252inches (6.4 mm) long by 0.30 inches (7.6 mm) wide. When pellet blastingwas repeated in a fresh area for sufficient time to damage theinterlayer of the polymer of Compound 4, n=4, the majority of theinterlayer was intact, with one ply of graphite composite material beingremoved in four places in the 1.655 inch (42.0 mm) long area. Thelargest depression on the interlayer was found to be 0.20 inch (5.1 mm)long by 0.15 inch (3.8 mm) composite material had been removedthroughout the bulk of the 1.2 inch (30.5 mm) long blasted area.

For panel B, it was found that the interlayer of the polymer of Compound4, n=4 was still intact after complete paint and primer removal of a 1.5inch (38.1 mm) long area, while extensive damage (removal of 5-12 pliesof the composite) to the unprotected side resulted. In particular, a0.237 inch (6.2 mm) by 0.373 inch (9.5 mm) hole through the compositewas made by the pellet blasting within a 1.684 inch (42.8 mm) long area.When the pellet blasting was repeated for a sufficient time to damagethe interlayer of the polymer of Compound 4, n=4, in a fresh area, thebulk of the 1.47 inch (37.4 mm) long area still had intact its coatingof the polymer of Compound 4, n=4, with a depression of 0.418 inches(10.6 mm) by 0.322 inch (8.2 mm) at the center of the panel, where 2-3plies of composite had been removed. On the unprotected side, extensivedamage (removal of 5 to 12 plies of composite) resulted. In particular,0.388-0.486 inch (9.9-12.3 mm) long by 0.934 inch (23.7 mm) wide holethrough the composite was made by the pellet blast.

This testing illustrates the excellent abrasion damage resistance of alayer of the polymer of Compound 4, n=4. Polymers of other compounds inaccordance with the present invention are expected to exhibit similarabrasion resistance. It is expected that coatings of polymers of thiscompound and its analogs will also exhibit good resistance to damage byplasma particles due to their unique chemical and physicalcharacteristics. Possible uses of these coatings in accordance with thepresent invention include that of a plasma mask and as abrasionresistant coatings or masks for aircraft and spacecraft applications. Inaddition, copolymers in accordance with the present invention whichexhibit appropriate toughness are also expected to exhibit goodresistance to mechanical or plasma abrasion.

As can be seen from the data presented in the Examples herein, thecompounds of the present invention provide resins which possess thermalstability, toughness, and low outgassing properties. By selection of theappropriate isomeric structure and chain length of the compounds of thepresent invention and selection of the appropriate hardener for curingthese compounds, the rigidity of the resulting structure may be tailoredanywhere within the range from soft rubbers to hard, tough plastics.These properties make the compounds of the present invention especiallyuseful for forming improved encapsulants, primers, topcoats, andadhesives for a variety of substrate materials, such as aluminum andgraphite-epoxy composites. In particular, due to the low outgassingproperties, the compounds of the present invention are well suited foruse in space applications. In addition, the epoxy monomer compounds ofthe present invention may be copolymerized with known epoxy resincoatings, adhesives, and encapsulants to toughen or to flexibilize them.Moreover, the ethenyl monomers of the present invention are useful forforming polymers and copolymers for applications as low dielectricmaterials. Finally, the polymers and copolymers of the present inventionare useful as abrasion-resistant coatings.

Having thus described exemplary embodiments of the present invention, itshould be noted by those skilled in the art that the disclosures withinare examplary only and that various other alternatives, adaptations andmodifications may be made within the scope of the present invention.Accordingly, the present invention is not limited to the specificembodiments as illustrated herein, but is only limited by the followingclaims.

What is claimed is:
 1. A polymer material formed by polymerization of acompound having the formula ##STR18## where R₁ is selected from thegroup consisting of (a) an aliphatic hydrocarbon group containing 2 to10 carbon atoms, and(b) a group having the formula ##STR19## where n=1to 3m=0 to 5;R₂ and R₂ ' are each selected from the group consisting ofan alkyl group containing 1 to 4 carbon atoms, an unsubstituted arylgroup, and a substituted aryl group; and R₃ is selected from the groupconsisting of: ##STR20## where R₄, R₅, and R₆ are each selected from thegroup consisting of H, an alkyl group containing 1 to 4 carbon atoms,and an aryl group; and n=0 to
 10. 2. A copolymer formed bypolymerizing:(1) a first monomer compound of the formula I: ##STR21##where R₁ is selected from the group consisting of: (a) an aliphatichydrocarbon group containing 2 to 10 carbon atoms, and(b) a group havingthe formula ##STR22## where n=1 to 3m=0 to 5; R₂ and R₂ ' are eachselected from the group consisting of an alkyl group containing 1 to 4carbon atoms, an unsubstituted aryl group, and a substituted aryl group;and R₃ is selected from the group consisting of: ##STR23## where R₄, R₅,and R₆ are each selected from the group consisting of H, an alkyl groupcontaining 1 to 4 carbon atoms, and an aryl group; and n=0 to 10, and(2) a second chosen monomer capable of copolymerization compound ofFormula I to form said copolymer.
 3. A copolymer according to claim 2wherein R₃ comprises ##STR24## where n=0 to 10, andsaid second monomeris selected from the group consisting of a compound having an epoxygroup and a compound having a siloxane group.
 4. A copolymer accordingto claim 2 wherein said compound of Formula I comprises 10 to 90 percentby weight of the mixture from which said copolymer is formed.
 5. Anarticle comprising a chosen substrate having formed on the surfacethereof a layer of the cured polymer set forth in claim
 1. 6. An articlecomprising a chosen substrate having formed on the surface thereof alayer of the cured copolymer set forth.
 7. A copolymer as set forth inclaim 3 comprising:(a) a predetermined amount within the range of 90 to20 percent by weight of said epoxy compound; and (b) a predeterminedamount within the range of 10 to 80 percent by weight of said compoundof formula I where R3 is attached to the phenylene group in the metaposition, wherein said copolymer has increased flexibility compared tothe polymerized product of said epoxy compound alone.
 8. A copolymeraccording to claim 7 wherein said predetermined amount of said compoundof formula I comprises about 30 to 50 percent by weight.
 9. A copolymeras set forth in claim 3 comprising:(a) a predetermined amount within therange of 90 to 20 percent by weight of said epoxy compound; and (b) apredetermined amount within the range of 10 to 80 percent by weight ofsaid compound of formula I where R3 is attached to the phenylene groupin the para position, wherein said copolymer has increased toughnesscompared to the polymerized product of said epoxy compound alone.
 10. Acopolymer according to claim 9 wherein said predetermined amount of saidcompound of formula I comprises about 30 to 50 percent by weight.